CN117222621A - Asymmetric methylenebisimides and their preparation - Google Patents
Asymmetric methylenebisimides and their preparation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 223
- 238000006243 chemical reaction Methods 0.000 claims description 58
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001448 anilines Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 7
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 6
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 6
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- SAPGIBGZGRMCFZ-UHFFFAOYSA-N 3-[(2,5-dioxopyrrol-3-yl)methyl]pyrrole-2,5-dione Chemical class O=C1NC(=O)C(CC=2C(NC(=O)C=2)=O)=C1 SAPGIBGZGRMCFZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- CQQUWTMMFMJEFE-UHFFFAOYSA-N 2-chloro-n,n-diethylacetamide Chemical compound CCN(CC)C(=O)CCl CQQUWTMMFMJEFE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 2
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- OHQOKJPHNPUMLN-UHFFFAOYSA-N n,n'-diphenylmethanediamine Chemical class C=1C=CC=CC=1NCNC1=CC=CC=C1 OHQOKJPHNPUMLN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- VPICDQPHVNYUMI-UHFFFAOYSA-N 4-[(1,3-dioxoisoindol-4-yl)methyl]isoindole-1,3-dione Chemical class O=C1NC(=O)C2=C1C=CC=C2CC1=CC=CC2=C1C(=O)NC2=O VPICDQPHVNYUMI-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to an asymmetric methylenebisimide of formula (I), a process for its preparation and its use in the preparation of resins.
Description
Technical Field
Asymmetric methylenebisimides, such as bismaleimides and methylenebisphthalimides, their preparation and their use in preparing resins are disclosed.
Background
There is an increasing demand for resins having application properties that meet the demands of high-end applications.
JP S6193159A discloses the use of bismaleimide derivatives for the preparation of resins.
EP 0544,266 a1 discloses a process for preparing symmetrical methylene bismaleimides.
There is a need for resins that exhibit good application properties, such as lower viscosity and better solvent solubility in combination with similar or lower reactivity than known methylene bismaleimide resins.
The reduced viscosity results in a reduced process temperature and thus a reduced energy consumption, which is both economically and environmentally advantageous. Reduced viscosity, increased solubility in common solvents, and/or low reactivity make processing easier.
Surprisingly, the asymmetric methylenebisimides of the present invention meet this need.
Abbreviations (abbreviations)
Alkyl straight or branched alkyl
asymmetry of asym
eq equivalent; unless otherwise indicated, equivalents are molar equivalents
Ex examples
sym symmetry
Disclosure of Invention
The subject of the invention is a process for preparing a compound of formula (I) by reaction (I) of a compound of formula (II) with maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic anhydride or 1,2,3, 6-tetrahydrophthalic anhydride:
wherein the method comprises the steps of
* And each represents a covalent bond with the corresponding C atom represented by the sum of residues (a);
(A) Is a residue of formula (M), a residue of formula (P), a residue of formula (Q), a residue of formula (O) or a residue of formula (T):
residues R2L, R3L, R6L, R2R, R R and R6R are the same or different and are independently selected from one another from the group consisting of H, C 1-4 Alkyl and Cl;
provided that in at least one of the following three pairs:
R2L and R2R
R3L and R3R
R6L and R6R
Are different residues.
Detailed Description
Preferably, R2, R3 and R6 are the same or different and are independently selected from the group consisting of: H. methyl, ethyl, n-propyl, isopropyl and Cl; more preferably, R2, R3 and R6 are the same or different and are independently selected from the group consisting of: H. methyl, ethyl, isopropyl and Cl.
In a further preferred embodiment, R2 and R6 are the same or different and are independently selected from the group consisting of: H. methyl, ethyl, n-propyl, isopropyl and Cl, while R3 is independently selected from the group consisting of: H. methyl, ethyl, n-propyl and isopropyl; more preferably, R2 and R6 are the same or different and are independently selected from the group consisting of: H. methyl, ethyl, isopropyl and Cl, and R3 is independently selected from the group consisting of: H. methyl, ethyl and isopropyl.
Preferably, the compound of formula (II) is reacted with maleic anhydride, citraconic anhydride, nadic anhydride or methyl-nadic anhydride, and (a) is a residue of formula (M), (Q), (O) or (T). Most preferably, the compound of formula (II) is reacted with maleic anhydride and (a) is a residue of formula (M).
Preferred embodiments of the compounds of formula (I) are selected from the group consisting of compounds of formula (IIIa; BMIDEAMEA), compounds of formula (IIIb; BMIDIPADEA), compounds of formula (IIIc; BMIDIPAMEA), compounds of formula (IIId; BMIMIPADEA), compounds of formula (IIIe; BMIMIPADIPA), compounds of formula (IIIf; BMIMIPAMEA), compounds of formula (IIIg; BMICDEMEA), compounds of formula (IIIh; BMICDEAMIPA), compounds of formula (IIIi; BMICDEADAPA) and compounds of formula (IIIj; BMICDEA).
More preferred embodiments of the compounds of formula (I) are selected from the group consisting of compounds of formula (IIIa; BMIDEAMEA), compounds of formula (IIIb; BMIDIPADEA), compounds of formula (IIIc; BMIDIPAMEA), compounds of formula (IIId; BMIMIPADEA), compounds of formula (IIIe; BMIMIPADIPA) and compounds of formula (IIIf; BMIMIPAMEA).
Preferably, the molar amount of maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic anhydride or 1,2,3, 6-tetrahydrophthalic anhydride is 2 to 4 times, more preferably 2 to 3 times, even more preferably 2 to 2.5 times the molar amount of the compound of formula (II).
The reaction (I) may be carried out in the presence of a catalyst (I); preferably, catalyst (I) is p-toluene sulfuric acid or p-toluene sulfuric acid monohydrate.
Preferably, the molar amount of catalyst (I) is from 0.1 to 1 times, more preferably from 0.2 to 0.9 times, even more preferably from 0.3 to 0.75 times the molar amount of the compound of formula (II).
The reaction (I) may be carried out in a solvent (I). Preferably, the solvent (I) is a nonpolar solvent capable of forming an azeotrope, preferably a positive azeotrope, with water. Solvents are generally considered to be nonpolar if they have a dielectric constant of 15 or less. A positive azeotrope is a mixture of solvents that exhibits a boiling point below that of any of its components. More preferably, solvent (I) is toluene, xylene isomers, or a mixture of any of the foregoing.
Preferably, the molar amount of solvent (I) is 5 to 50 times, more preferably 10 to 30 times the molar amount of the compound of formula (II).
Preferably, reaction (I) is carried out at a reaction temperature of from 50 to 200 ℃, more preferably from 75 to 175 ℃, even more preferably from 100 to 175 ℃, especially from 120 to 160 ℃.
Preferably, the reaction time of reaction (I) is from 1 to 12 hours, more preferably from 2.5 to 10 hours, even more preferably from 3 to 8 hours.
Reaction (I) may be carried out at ambient or elevated pressure. For example, when reaction (I) is carried out in solvent (I) and the temperature is selected to be higher than the boiling point of solvent (I), an elevated pressure is applied.
After reaction (I), the compound of formula (I) may be isolated according to standard methods known to the person skilled in the art, for example by removing any solvent (I) used, preferably by distillation; adjusting the pH to an alkaline pH by adding a base, preferably sodium hydroxide, more preferably an aqueous solution of sodium hydroxide; separating any aqueous phase from the organic phase; washing the organic phase with water; any solvent is removed from the organic phase, preferably by distillation.
Preferably, the compounds of formula (II) are prepared by reacting a compound of formula (Iva; AML) and a compound of formula (IVb; AMR) with formaldehyde (II);
wherein the method comprises the steps of
R2L, R3L, R6L, R2R, R R and R6R and all embodiments thereof are as defined herein.
In one embodiment, the compound of formula (II) prepared by reaction (II) is obtained as mixture (I). Mixture (I) is a mixture of a compound of formula (II) with a compound of formula (Va; BISL) and a compound of formula (Vb; BISR);
wherein R2L, R3L, R6L, R2R, R R and R6R and all embodiments thereof are as defined herein.
Preferred embodiments of the compounds of formula (Va; BISL) and of the compounds of formula (Vb; BISR) are selected from the group consisting of compounds of formula (VIa; bisdiea), compounds of formula (VIb; bisiipa), compounds of formula (VIc; bisiipa), compounds of formula (VId; bisdiea) and compounds of formula (VIe; BISCDEA):
more preferred embodiments of the compounds of formula (Va; BISL) and the compounds of formula (Vb; BISR) are selected from the group consisting of: a compound of formula (VIa; BISDEA), a compound of formula (VIb; BISDIPA), a compound of formula (VIc; BISMPA) and a compound of formula (VId; BISMEA).
Reaction (II) is the condensation of compounds of formula (IVa) and (IVb) with formaldehyde.
The compounds of the formula (Va; BISL) are symmetrically substituted and are obtained by reaction (III) of 1eq of formaldehyde with 2eq of the compound of the formula (IVa), the reaction (III) taking place as a side reaction in reaction (II).
The compound of formula (Vb; BISR) is symmetrically substituted and is obtained by reaction (IV) of 1eq formaldehyde with 2eq of a compound of formula (IVb; AMR), the reaction (IV) taking place as a side reaction in reaction (II).
In one embodiment, the compounds of formula (II) are used in reaction (I) in the form of a mixture (I).
Preferably, mixture (I) comprises the compound of formula (II) in an amount of at least 30wt%, at least 40wt%, at least 50wt%, at least 60wt%, at least 70wt% or at least 80wt%, more preferably at least 40wt% or at least 50wt%, most preferably at least 40wt%.
When the compound of formula (II) is used in the form of mixture (I) for reaction (I), then the compound of formula (I) is obtained from reaction (I) in the form of mixture (II). Mixture (II) is a mixture of a compound of formula (I) with a compound of formula (VIIa; BMIL) and a compound of formula (VIIb; BMIR);
wherein R2L, R3L, R6L, R2R, R R and R6R and all embodiments thereof are as defined herein.
Preferred embodiments of the compounds of formula (VIIa; BMIL) and formula (VIIb; BMIR) are selected from the group consisting of compounds of formula (VIIIa; BMIDEA), formula (VIIIb; BMIDIPA), formula (VIIIc; BMIMIPA), formula (VIIId; BMIMEA) and formula (VIIIe; BMICDEA):
more preferred embodiments of the compounds of formula (VIIa; BMIL) and the compounds of formula (VIIb; BMIR) are selected from the group consisting of: compounds of formula (VIIIa; BMIDEA), formula (VIIIb; BMIDIPA), formula (VIIIc; BMIMIPA) and formula (VIIId; BMIMEIA).
Preferably, mixture (II) comprises the compound of formula (I) in an amount of at least 20wt%, at least 30wt%, at least 40wt%, at least 50wt%, at least 60wt% or at least 70wt%, more preferably at least 30wt% or at least 40wt%, most preferably at least 30wt%.
In another embodiment, the compound of formula (II) is used in reaction (I) in a substantially pure form, i.e., it comprises less than 30wt%, less than 20wt%, less than 10wt% or less than 5wt% of the total amount of the compounds of formula (Va; BISL) and the compounds of formula (Vb; BISR).
The molar ratio of the compound of formula (IVa) to the compound of formula (IVb) may vary within a wide range; preferably, the molar amounts of the compound of formula (IVa) and the compound of formula (IVb) are comparable. Thus, the molar ratio of the compound of formula (IVa) to the compound of formula (IVb) is from 4:1 to 1:4, more preferably from 2:1 to 1:2, even more preferably from 1.5:1 to 1:1.5, in particular from 1.3:1 to 1:1.3.
The choice of the compounds of formula (IVa) and (IVb) in reaction (II) determines what specific mixture (I) is obtained from reaction (II); and the choice of mixture (I) in reaction (I) determines what specific mixture (II) is obtained from reaction (I).
Table 1 shows preferred combinations of compounds of formula (IVa; AML) and compounds of formula (IVb; AMR) and of the mixture (I) obtained from reaction (II) and of the compounds obtained from reaction (I) in mixture (II).
More preferred combinations of compounds of formula (IVa; AML) and compounds of formula (IVb; AMR) according to Table 1 do not contain CDEA (Xe).
The formaldehyde may be in the form of formalin solution, paraformaldehyde or trioxane, or free or bound formaldehyde in other well known forms that form formaldehyde.
Preferably, formaldehyde is used in the form of an aqueous solution.
More preferably, formaldehyde is used in the form of an aqueous solution containing 20 to 40wt%, more preferably 30 to 40wt% formaldehyde.
Preferably, the molar amount of formaldehyde is from 0.5 to 0.7 times, more preferably from 0.5 to 0.6 times, even more preferably from 0.5 to 0.55 times the combined molar amount of the compound of formula (IVa) and the compound of formula (IVb).
Preferably, reaction (II) is carried out in an acidic medium.
Preferably, reaction (II) is carried out in the presence of catalyst (II); preferably, catalyst (II) is sulfuric acid.
Preferably, the molar amount of catalyst (II) is from 0.8 to 1 times, more preferably from 0.85 to 1 times, even more preferably from 0.85 to 0.95 times the combined molar amount of the compound of formula (IVa) and the compound of formula (IVb).
The reaction (II) may be carried out in a solvent (II); preferably, the solvent (II) is isopropanol.
Preferably, the molar amount of solvent (II) is from 1 to 50 times, more preferably from 1.5 to 30 times, even more preferably from 1.5 to 15 times, especially from 1.5 to 10 times, more preferably from 1.5 to 7.5 times, even more especially from 1.5 to 5 times the combined molar amount of the compound of formula (IVa) and the compound of formula (IVb).
Preferably, reaction (II) is carried out at a reaction temperature of from 40 to 200 ℃, more preferably from 50 to 175 ℃, even more preferably from 50 to 150 ℃, especially from 50 to 125 ℃, more especially from 50 to 100 ℃, even more especially from 50 to 75 ℃.
Preferably, the reaction time of reaction (II) is from 1 to 12 hours, more preferably from 2.5 to 10 hours, even more preferably from 4 to 8 hours.
Reaction (II) may be carried out at ambient or elevated pressure. For example, when reaction (II) is carried out in solvent (II) and the selected temperature is higher than the boiling point of solvent (II), an elevated pressure is applied.
After reaction (II), the compound of formula (II) may be isolated according to standard methods known to the person skilled in the art, for example by removing any solvent (I) used, preferably by distillation; adjusting the pH to an alkaline pH by adding a base, preferably sodium hydroxide, more preferably an aqueous solution of sodium hydroxide; separating any aqueous phase from the organic phase; washing the organic phase with water; any solvent is removed from the organic phase, preferably by distillation.
Preferred embodiments of the compound of formula (II) are selected from the group consisting of a compound of formula (IXa; BISDEAMEA), a compound of formula (IXb; BISDIPAEEA), a compound of formula (IXc; BISDIPIAMEA), a compound of formula (IXd; BISMIPIAEA), a compound of formula (IXe; BISMIPIAPAIPA), a compound of formula (IXf; BISMIPAEMA), a compound of formula (IXg; BISCDEAEA), a compound of formula (IXh; BISCDEAPA), a compound of formula (IXi; BISCDEADAPA) and a compound of formula (IXj; BISCDEADA).
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More preferred embodiments of the compounds of formula (II) are selected from the group consisting of: a compound of formula (IXa; BISDEAMEA), a compound of formula (IXb; BISDIPAEMA), a compound of formula (IXc; BISDIPAEMA), a compound of formula (IXd; BISMIPAEA), a compound of formula (IXe; BISMIPAPAPAPPA) and a compound of formula (IXf; BISMIPAEMA).
Preferred embodiments of the compounds of formula (IVa) and (IVb) are selected from the group consisting of compounds of formula (Xa; MEA), compounds of formula (Xb; DEA), compounds of formula (Xc; DIPA), compounds of formula (Xd; MIPA) and compounds of formula (Xe; CDEA):
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more preferred embodiments of the compounds of formula (IVa) and (IVb) are selected from the group consisting of compounds of formula (Xa; MEA), compounds of formula (Xb; DEA), compounds of formula (Xc; DIPA) and compounds of formula (Xd; MIPA).
In reaction (II), there may be present further anilines, preferably 1,2 or 3 further anilines, for example compounds of the formula (XI; AM), which are different from the compounds of the formula (IVa) and the compounds of the formula (IVb);
wherein R2, R3 and R6 are the same or different and are independently selected from the group consisting of H, C 1-4 Alkyl and Cl, preferably wherein R2 and R6 are identical or different and are each otherIndependently selected from H, C 1-4 Alkyl and C1, and R3 is selected from the group consisting of H or C1-4 alkyl.
The presence of such additional anilines in reaction (II) results in a corresponding mixture of asymmetric methylene-bis-anilines with corresponding symmetric methylene-bis-anilines, which can be obtained from any combination of the two anilines of all anilines present in reaction (II);
the use of such mixtures in reaction (I) yields the corresponding mixtures of asymmetric methylene-bis-maleimides with symmetric methylene-bis-maleimides.
Table 2 shows embodiments in which three anilines are used in reaction (II), and thus the mixture obtained from reaction (II) and subsequently from reaction (I).
Another subject of the invention is a compound of formula (I); wherein the compound of formula (I) and all embodiments thereof are as defined herein.
Another subject of the invention is a mixture of a compound of formula (I) with a compound of formula (VIIa; BMIL) and a compound of formula (VIIb; BMIR); wherein the compound of formula (I), the compound of formula (VIIa; BMIL) and the compound of formula (VIIb; BMIR) and all embodiments thereof are as defined herein.
Another subject of the invention is the use of a compound of formula (I) for the preparation of a resin; wherein the compound of formula (I) and all embodiments thereof are as defined herein.
Examples
Abbreviations:
a1 Amine 1
A2 Amine 2
A3 Amine 3
Melting Point of Mp
p-Tos p-toluenesulfonic acid monohydrate
wt% wt
Yd yield
MEK methyl ethyl ketone
DMF N, N-dimethylformamide
Material
Maleic anhydride CAS108-31-6, > = 99.0%, sigma-Aldrich
P-toluenesulfonic acid monohydrate CAS 6192-52-5, > = 98%, sigma-Aldrich
Method
(1)GC
Instrument parameters
Chromatographic column OPTIMA-1 (30m x 0.32mm x 0.35 micron)
Temperature program:
initial temperature, time: 90 ℃;0 min
Rate 1, final temperature 1, time 1:30 ℃/min; 200 ℃;0 min
Rate 2, final temperature 2, time 2:20 ℃/min; 260 ℃;0 min
Rate 3, final temperature 3, time 3:2 ℃/min; 280 ℃;0.33 min
Run time 17.00 minutes
Equilibration time 3 min
Mode constant current
Carrier gas H 2
Flow 2.0 mL/min
Split ratio 50:1
The inlet temperature is 250 DEG C
Sample injection amount 1 microliter (mu L)
A detector: FID (FID)
The temperature of the detector is 320 DEG C
Sample preparation:
the sample was heated to 50 ℃, 200mg of the sample was added to 1mL of methanol in a 2mL GC vial, and homogenized by shaking.
(2) HPLC-UVLHPLC-UV is reverse phase HPLC using UV detection.
Column: xbridge Shield 150mm x 3.0mm x 3.5 μm or the like
And (3) a pump:
minimum pressure: 5 bar
Maximum pressure: 400 bar
Maximum flow gradient: 100 mL/min eluent A:20mmol ammonium acetate aqueous solution pH 3.0
Eluent B: acetonitrile
And (3) sample injection:
sample injection amount 10 microliters (mu L)
A detector:
detector type UV
Wavelength 269nm
Column incubator:
at a temperature of 40 DEG C
Sample preparation:
20mg +/-4mg of the sample was dissolved in 20mL of acetonitrile.
LOD (limit of detection) is 0.02 area-%.
LOQ (limit of quantitation) is 0.07 area-%.
(3) Yield calculation:
the percentage determined by GC or HPLC chromatograms is the area percentage of the corresponding signal.
The respective reaction yields of the mixtures are calculated on the basis of the sum of the molar masses of each individual compound in the mixture multiplied by the respective area% content determined by GC or HPLC, respectively.
General procedure 1: preparation of the Mixed Compounds of formula (II)
A mixture of different aromatic amines (about 2mol eq total, see tables 1A, 1B and 1C for specific equivalent) was dissolved in propan-2-ol (4.73 mol eq) and water (2.16 mol eq). Sulfuric acid (96.0 wt%,1.81mol eq) was added to the stirred mixture and the mixture was heated to 60 ℃. An aqueous formaldehyde solution (37 wt%,1.08mol eq) was added through the dip tube over a period of 1 hour. The reaction mixture was then stirred at 60 ℃ for 5 hours. The temperature was adjusted to 25℃and aqueous sodium hydroxide (25 wt%,3.80mol eq) was added. The product was extracted with chloroform and then washed with water. The organic phase is separated and the organic solvent is completely removed under vacuum, giving a mixture of symmetrical (sym) and asymmetrical (asym) compounds of formula (II) as a brown melt.
Tables 4A, 4B and 4C show examples prepared according to the general procedure.
General procedure 2: preparation of the Mixed Compounds of formula (I)
A melt of the mixed compound of formula (II) (1 mol eq, prepared according to general procedure 1) was dissolved in xylene (17 mol eq) to provide a solution of the mixed compound of formula (II) in xylene. In a reactor equipped with a dean-Stark trap, xylene (17 mol eq) was added, and p-toluene sulfuric acid monohydrate (0.46 mol eq) and maleic anhydride (2.30 mol eq) were dissolved. The mixture was heated to reflux. A previously prepared solution of the compound of formula (II) in xylene was added over 1 hour while maintaining the reaction mixture at reflux. After dosing the xylene solution of the mixed compound of formula (II), the reaction mixture is kept at reflux until no more water is collected in the dean-stark trap, typically for 3 to 5 hours. About 20% by volume of the xylenes were then removed by distillation.
The temperature was adjusted to 90℃and aqueous sodium hydroxide (10 wt%,5.7mol eq) was added. The mixture was stirred at 90℃for 30 minutes. The aqueous phase is separated and the organic phase is subsequently washed with 3 parts of water (4 mol eq per part). The organic phase is separated and the organic solvent is completely removed under vacuum to give the compound of formula (I) as a brown melt.
Table 5 shows examples prepared according to general procedure 2.
(4) Solubility analysis:
the solubility was determined using a Metler tolidol halogen dryer (Mettler-Toledo GmbH; germany Ji Sen). Saturated solutions of each compound were prepared in the respective solvents, and the amount of dissolution (wt%) in the liquid phase was measured after filtration using a syringe filter (1 μ pore size) on a halogen dryer. The results of the solubility analysis are summarized in Table 6 (BMPI-300 is a 1:1 mixture of BMIDEA (formula VIIIa) and BMIMIPA (formula VIIIc; BMI-5100 is BMIMEA (formula VIIId)).
This is an emulsion, not a clear solution
(5) Gel time analysis:
according to the manufacturer's instructions, useGel timer (tavern, switzerland Gel lnstrumente AG) measured gel time. The results of the solubility analysis are summarized in table 7.
(6) Viscosity analysis:
the viscosity was determined using a Brookfield LV-II-Pro viscometer (BROOKFIELD ENGINEERING LABORATORIES, INC.; middleboro, midberger, mass.) with a Thermosel system according to the manufacturer's instructions. The results of the solubility analysis are summarized in table 8 (dashed lines indicate temperatures below the melting point). The compounds of formula (I) according to the invention are observed to have a lower viscosity than the eutectic mixtures of the corresponding symmetrical bismaleimide derivatives.
TABLE 8
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Claims (15)
1. A process for preparing a compound of formula (I) by reacting a compound of formula (II) with maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic anhydride or 1,2,3, 6-tetrahydrophthalic anhydride:
wherein the method comprises the steps of
* And each represents a covalent bond with the corresponding C atom represented by the sum of residues (a);
(A) Is a residue of formula (M), a residue of formula (P), a residue of formula (Q), a residue of formula (O) or a residue of formula (T):
residues R2L, R3L, R6L, R2R, R R and R6R are the same or different and are independently selected from one another from the group consisting of H, C 1-4 Alkyl and Cl;
provided that in at least one of the following three pairs:
R2L and R2R
R3L and R3R
R6L and R6R
Are different residues; and is also provided with
Wherein R2, R3 and R6 are the same or different and are independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl and Cl.
2. The method according to claim 1, wherein:
(i) R2, R3 and R6 are identical or different and are independently selected from the group consisting of:
ii. Methyl, ethyl, isopropyl and Cl; and/or
(ii) Reacting the compound of formula (II) with maleic anhydride, citraconic anhydride, nadic anhydride, or methyl-nadic anhydride, and (a) is a residue of formula (M), (Q), (O), or (T).
3. The method of any of the preceding claims, wherein the compound of formula (I) is selected from the group consisting of a compound of formula (IIIa), a compound of formula (IIIb), a compound of formula (IIIc), a compound of formula (IIId), a compound of formula (IIIe), a compound of formula (IIIf), a compound of formula (IIIg), a compound of formula (IIIh), a compound of formula (IIIi), and a compound of formula (IIIj):
4. the method of any one of the preceding claims, wherein the compound of formula (II) is selected from the group consisting of a compound of formula (IXa), a compound of formula (IXb), a compound of formula (IXc), a compound of formula (IXd), a compound of formula (IXe), a compound of formula (IXf), a compound of formula (IXg), a compound of formula (IXh), a compound of formula (IXi), and a compound of formula (IXj):
5. the method of any one of the preceding claims, wherein
a) The molar amount of maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic anhydride or 1,2,3, 6-tetrahydrophthalic anhydride is 2 to 4 times the molar amount of the compound of formula (II);
b) Wherein the reaction (I) is carried out in the presence of a catalyst (I); optionally, wherein
(i) The catalyst (I) is p-toluenesulfonic acid or p-toluenesulfonic acid monohydrate; and/or
(ii) The molar amount of catalyst (I) is from 0.1 to 1 times the molar amount of compound of formula (II);
c) The reaction (I) is carried out in a solvent (I); optionally, wherein
(i) Solvent (I) is a nonpolar solvent capable of forming an azeotrope with water; and/or
(ii) The molar amount of solvent (I) is 5 to 50 times the molar amount of the compound of formula (II);
d) The reaction (I) is carried out at a reaction temperature of 50 to 200 ℃; and/or
e) The reaction time of reaction (I) is 1 to 12 hours.
6. The process according to any one of the preceding claims, wherein the compound of formula (II) is prepared by reaction (II) of a compound of formula (IVa) and a compound of formula (IVb) with formaldehyde;
wherein the method comprises the steps of
R2L, R3L, R6L, R2R, R3R and R6R are as defined in any one of claims 1 or 2 (i);
optionally, wherein
The compound of formula (IVa) and the compound of formula (IVb) are selected from the group consisting of a compound of formula (Xa), a compound of formula (Xb), a compound of formula (Xc), a compound of formula (Xd) and a compound of formula (Xe):
7. the process of claim 6, wherein the compound of formula (II) is obtained as mixture (I), wherein mixture (I) is a mixture of a compound of formula (II) with a compound of formula (Va) and a compound of formula (Vb);
wherein R2L, R3L, R6L, R2R, R3R and R6R are as defined in any one of claims 1 or 2 (i);
optionally wherein
The compound of formula (Va) and the compound of formula (Vb) are selected from the group consisting of a compound of formula (VIa), a compound of formula (VIb), a compound of formula (VIc), a compound of formula (VId) and a compound of formula (VIe):
8. the process according to any one of the preceding claims, wherein the compound of formula (II) is used in reaction (I) in the form of a mixture (I), wherein the compound of formula (I) is obtained in the form of a mixture (II), wherein mixture (II) is a mixture of the compound of formula (I) with the compound of formula (VIIa) and the compound of formula (VIIb);
wherein R2L, R3L, R6L, R2R, R R and R6R are as defined in any one of claims 1 or 2 (i); optionally, wherein
The compound of formula (VIIa) and the compound of formula (VIIb) are selected from the group consisting of a compound of formula (VIIIa), a compound of formula (VIIIb), a compound of formula (VIIIc), a compound of formula (VIIId), and a compound of formula (VIIIe):
9. the method of any one of claims 6 to 8, wherein the molar ratio of the compound of formula (IVa) to the compound of formula (IVb) is from 4:1 to 1:4.
10. The method according to any one of claims 8 or 9, wherein the compound of formula (IVb) and the compound of formula (IVa) are as defined in table a, resulting in a mixture (II) comprising the compounds as defined in table a.
11. The method according to any one of claims 6-10, wherein
a) Formaldehyde is in the form of formalin solution, paraformaldehyde or trioxane;
b) The formaldehyde is used in the form of an aqueous solution, optionally in the form of an aqueous solution containing 20 to 40wt% formaldehyde;
c) The molar amount of formaldehyde is from 0.5 to 0.7 times the combined molar amount of the compound of formula (IVa) and the compound of formula (IVb);
d) Reaction (II) is carried out in an acidic medium;
e) The reaction (II) is carried out in the presence of a catalyst (II); optionally, wherein
(i) The catalyst (II) is sulfuric acid; and/or
(ii) The molar amount of catalyst (II) is from 0.8 to 1 times the combined molar amount of compound of formula (IVa) and compound of formula (IVb);
f) The reaction (II) is carried out in a solvent (II); optionally, wherein
(i) The solvent (II) is isopropanol; and/or
(ii) The molar amount of solvent (II) is 1 to 50 times the combined molar amount of the compound of formula (IVa) and the compound of formula (IVb);
g) The reaction (II) is carried out at a reaction temperature of 40 to 200 ℃; and/or
h) The reaction time of reaction (II) is 1 to 12 hours.
12. The process according to any one of claims 6 to 11, wherein in reaction (II) there is an additional aniline, optionally wherein there are 1,2 or 3 additional anilines, further optionally wherein the additional anilines are compounds of formula (XI) which are different from the compounds of formula (IVa) and the compounds of formula (IVb);
wherein R2, R3 and R6 are the same or different and are independently selected from the group consisting of H, C 1-4 Alkyl and Cl.
13. A compound of formula (I):
wherein the compound of formula (I) is as defined in any one of claims 1 to 3.
14. Mixtures of compounds of formula (I) with compounds of formula (VIIa) and compounds of formula (VIIb); wherein the compound of formula (I) is as defined in any one of claims 1 to 3 and the compounds of formula (VIIa) and (VIIb) are as defined in claim 8.
15. The use of a compound of formula (I) for the preparation of a resin,
wherein the compound of formula (I) is as defined in any one of claims 1 to 3.
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| EP21169409 | 2021-04-20 | ||
| EP21169409.6 | 2021-04-20 | ||
| PCT/EP2022/059096 WO2022223295A1 (en) | 2021-04-20 | 2022-04-06 | Asymmetrical methylene bis imides and their preparation |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130564A (en) * | 1976-04-09 | 1978-12-19 | Ciba-Geigy Corporation | Process for the manufacture of maleimides |
| JPS6193159A (en) * | 1984-10-15 | 1986-05-12 | Mitsubishi Petrochem Co Ltd | Bismaleimide |
| JPH0431464A (en) * | 1990-05-25 | 1992-02-03 | Mitsubishi Petrochem Co Ltd | Curing resin composition for circuit and metal foil-clad resin board |
| CN1072678A (en) * | 1991-11-28 | 1993-06-02 | 瑞士隆萨股份公司 | Produce the method for bimaleimide derivatives |
| KR20150002953A (en) * | 2013-06-27 | 2015-01-08 | 제일모직주식회사 | Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns including the patterns |
-
2022
- 2022-04-06 JP JP2023564136A patent/JP2024515679A/en active Pending
- 2022-04-06 CN CN202280029490.0A patent/CN117222621A/en active Pending
- 2022-04-06 WO PCT/EP2022/059096 patent/WO2022223295A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130564A (en) * | 1976-04-09 | 1978-12-19 | Ciba-Geigy Corporation | Process for the manufacture of maleimides |
| JPS6193159A (en) * | 1984-10-15 | 1986-05-12 | Mitsubishi Petrochem Co Ltd | Bismaleimide |
| JPH0431464A (en) * | 1990-05-25 | 1992-02-03 | Mitsubishi Petrochem Co Ltd | Curing resin composition for circuit and metal foil-clad resin board |
| CN1072678A (en) * | 1991-11-28 | 1993-06-02 | 瑞士隆萨股份公司 | Produce the method for bimaleimide derivatives |
| KR20150002953A (en) * | 2013-06-27 | 2015-01-08 | 제일모직주식회사 | Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns including the patterns |
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